Abstract
Development of advanced supercapacitors which provide greater energy density while retaining high power density can revolutionize energy storage solutions for both civilian and military applications. Herein, we present fabrication and characterization of nanostructured supercapacitor electrodes using manganese dioxide and carbon nanotubes (MnO2/CNTs) on flexible graphite foil substrate for integration into a supercapacitor prototype cell, without any additives or binders. Low-cost, thermal chemical vapor deposition process in a tube furnace was used to synthesize CNTs, acting as the current conductors, directly on both sides of the flexible, conducting graphite foil current collector. Thin-film MnO2 deposition on the CNTs was achieved by electrochemical technique using in situ reduction of potassium permanganate (KMnO4), without any supporting electrolyte, which provides excellent bonding between the two for enhanced stability. Eight electrodes were assembled in a stack with polypropylene separators and packaged in a pouch cell with organic electrolyte (1 M tetraethylammonium tetrafluoroborate in acetonitrile) yielding a total capacitance of nearly 2.8 F at 2.5 V and a corresponding specific capacitance of 388 F g−1 was calculated for MnO2. High cell capacitance and a low DC resistance yield a maximum specific power value of 36.1 kW kg−1 and a maximum specific energy of 48.5 Wh kg−1 at 2.5 V when considering the total mass including that of CNTs and MnO2. Cycling data showed nearly 100% capacitance retention over 3000 charge discharge cycles. To the best of our knowledge, a supercapacitor prototype cell in this configuration has not been fabricated and/or reported previously.
Graphical Abstract
Schematic representation of the prototype supercapacitor cell consisting of a stack of eight electrodes with polypropylene separators. On the right is a blow-up representation of a double side electrode with MnO2/CNT on both sides of the graphite foil substrate. The equivalent circuit diagram can be seen on the left, consisting of seven capacitors in parallel
Similar content being viewed by others
References
Cheng Q, Ma J, Zhang H, Shinya N, Qin L, Tang J (2010) Electrodeposition of MnO2 on carbon nanotube thin films as flexible electrodes for supercapacitors. Trans Mater Res Soc Jpn 35(2):369–372. doi:10.14723/tmrsj.35.369
Wang Y (2012) Manganese dioxide based composite electrodes for electrochemical supercapacitors. Doctoral Dissertation, McMaster University
Yu G, Xie X, Pan L, Bao Z, Cui Y (2013) Hybrid nanostructured materials for high-performance electrochemical capacitors high-performance electrochemical capacitors. Nano Energy 2(2):213–234. doi:10.1016/j.nanoen.2012.10.006
Akbulut S (2011) Optimization of carbon nanotube supercapacitor electrode. Master’s Thesis, Vanderbilt University
Li J, Cheng X, Shashurin A, Keidar M (2012) Review of electrochemical capacitors based on carbon nanotubes and graphene. Graphene 01(01):1–13. doi:10.4236/graphene.2012.11001
Caglar B (2010). Production of carbon nanotubes by PECVD and their applications to supercapacitors. Master’s Thesis, Universitat de Barcelona
Wei S (2009) Field emitters and supercapacitors based on carbon nanotube films. Doctoral Dissertation, Vanderbilt University
Anton CM, Ervin MH (2011) Carbon nanotube based flexible supercapacitors. Tech. No. ARL-TR-5522
Malmberg H (2007) Nanoscientific investigations of electrode materials for supercapacitors. Doctoral Dissertation, Kungliga Tekniska Högskolan
Guittet M, Aria AI, Gharib M (2011) Use of vertically-aligned carbon nanotube array to enhance the performance of electrochemical capacitors. In: 2011 11th IEEE international conference on nanotechnology. doi:10.1109/nano.2011.6144354
Shanov V, Yun Y, Shulz MJ (2006) Synthesis and characterization of carbon nanotube materials. J Univ Chem Technol Metall 35(4):377–390
Lan Y, Wang Y, Ren ZF (2011) Physics and applications of aligned carbon nanotubes. Adv Phys 60(4):553–678. doi:10.1080/00018732.2011.599963
Liu W, Yan X, Lang J, Peng C, Xue Q (2012) Flexible and conductive nanocomposite electrode based on graphene sheets and cotton cloth for supercapacitor. J Mater Chem 22(33):17245. doi:10.1039/c2jm32659k
Chen J, Li W, Wang D, Yang S, Wen J, Ren Z (2002) Electrochemical characterization of carbon nanotubes as electrode in electrochemical double-layer capacitors. Carbon 40(8):1193–1197. doi:10.1016/s0008-6223(01)00266-4
Augustyn V et al (2013) High-rate electrochemical energy storage through Li intercalation pseudocapacitance. Nat Mater 12(6):518–522. doi:10.1038/nmat3601
Wu N (2002) Nanocrystalline oxide supercapacitors. Mater Chem Phys 75(1–3):6–11. doi:10.1016/s0254-0584(02)00022-6
Boukhalfa S, Evanoff K, Yushin G (2012) Atomic layer deposition of vanadium oxide on carbon nanotubes for high-power supercapacitor electrodes. Energy Environ Sci 5(5):6872. doi:10.1039/c2ee21110f
Dong X, Shen W, Gu J, Xiong L, Zhu Y, Li H, Shi J (2006) MnO2-embedded-in-mesoporous-carbon-wall structure for use as electrochemical capacitors. J Phys Chem B 110(12):6015–6019. doi:10.1021/jp056754n
Lu Z et al (2012) Hierarchical Co3O4@Ni-Co-O supercapacitor electrodes with ultrahigh specific capacitance per area. Nano Res 5(5):369–378. doi:10.1007/s12274-012-0217-2
Brezesinski T, Wang J, Tolbert SH, Dunn B (2010) Ordered mesoporous α-MoO3 with iso-oriented nanocrystalline walls for thin-film pseudocapacitors. Nat Mater 9(2):146–151. doi:10.1038/nmat2612
Kiamahalleh MV, Zein SH, Najafpour G, Sata SA, Buniran S (2012) Multiwalled carbon nanotubes based nanocomposites for supercapacitors: a review of electrode materials. NANO 07(02):1230002. doi:10.1142/s1793292012300022
Wei W, Cui X, Chen W, Ivey DG (2011) Manganese oxide-based materials as electrochemical supercapacitor electrodes. Chem Soc Rev 40(3):1697–1721. doi:10.1039/c0cs00127a
Hu L et al (2011) Symmetrical MnO2–carbon nanotube-textile nanostructures for wearable pseudocapacitors with high mass loading. ACS Nano 5(11):8904–8913. doi:10.1021/nn203085j
Xiao F, Xu Y (2012) Electrochemical co-deposition and characterization of MnO2/SWNT composite for supercapacitor application. J Mater Sci Mater Electron 24(6):1913–1920. doi:10.1007/s10854-012-1034-9
Hou Y, Cheng Y, Hobson T, Liu J (2010) Design and synthesis of hierarchical MnO2 nanospheres/carbon nanotubes/conducting polymer ternary composite for high performance electrochemical electrodes. Nano Lett 10(7):2727–2733. doi:10.1021/nl101723g
Zhao J, Lu Z, Shao M, Yan D, Wei M, Evans DG, Duan X (2013) Flexible hierarchical nanocomposites based on MnO2 nanowires/CoAl hydrotalcite/carbon fibers for high-performance supercapacitors. RSC Adv 3(4):1045–1049. doi:10.1039/c2ra22566b
Teng F, Santhanagopalan S, Meng DD (2010) Microstructure control of MnO2/CNT hybrids under in situ hydrothermal conditions. Solid State Sci 12(9):1677–1682. doi:10.1016/j.solidstatesciences.2010.07.026
Yan Z, Hao Z, Yajuan X, Yuexin D (2010) Studies of electromagnetic properties of MWCNTs after electroless plating with Co-Fe alloy. Chin J Aeronaut 23(3):377–380. doi:10.1016/s1000-9361(09)60230-2
Lu W, Henry K, Turchi C, Pellegrino J (2008) Incorporating ionic liquid electrolytes into polymer gels for solid-state ultracapacitors. J Electrochem Soc 155(5):A361–A367. doi:10.1149/1.2869202
Chen Y, Hsu Y, Lin Y, Chen L, Chen K (2012) Spontaneous synthesis and electrochemical characterization of nanostructured MnO2 on nitrogen-incorporated carbon nanotubes. Int J Electrochem 2012:1–10. doi:10.1155/2012/475417
Gao T, Fjellvåg H, Norby P (2009) A comparison study on Raman scattering properties of α- and β-MnO2. Anal Chim Acta 648(2):235–239. doi:10.1016/j.aca.2009.06.059
Xiao C, Chen J, Liu B, Chu X, Wu L, Yao S (2011) Sensitive and selective electrochemical sensing of l-cysteine based on a caterpillar-like manganese dioxide–carbon nanocomposite. Phys Chem Chem Phys 13(4):1568–1574. doi:10.1039/c0cp00980f
Buciuman F, Patcas F, Craciun R, Zahn DR (1999) Vibrational spectroscopy of bulk and supported manganese oxides. Phys Chem Chem Phys 1(1):185–190. doi:10.1039/a807821a
Akbulut S, Yilmaz M, Raina S, Hsu S-H, Kang WP (2017) Solid-state supercapacitor cell based on 3D nanostructured MnO2/CNT microelectrode array on graphite and H3PO4/PVA electrolyte. Diamond Relat Mater 74:222–228. doi:10.1016/j.diamond.2017.03.016
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Akbulut, S., Yilmaz, M., Raina, S. et al. Advanced supercapacitor prototype using nanostructured double-sided MnO2/CNT electrodes on flexible graphite foil. J Appl Electrochem 47, 1035–1044 (2017). https://doi.org/10.1007/s10800-017-1098-6
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10800-017-1098-6